Process of obtaining proteo-cellulosic products.



UNITED STATES PATENT OFFICE.

HENBI IiOUIS JOSEPH CHAVASSIEU, O'F LYON, FRANCE.

PROCESS OF OBTAINING PROTEO-CELLULOSIC PRODUCTS.

N 0 Drawing. 7

Specification of Letters'ratent. Patent .ed Fol), 22, fl 910. Application filed December 22, 1908. Serial No. 468,722. (Specimens) To all whom 'it may concern:

Be it known that l, HENRI LOUIS Josnrn (lnamssn-zc, a citizen of the French Repubproteids and the application of the resulting products to industrial purposes.

The. process is for the purpose of obtaining new soluble and coagulable compositions of proteid substances known alsoas albuminoiils," and to apply these compositions to various industrial uses, and especially to those uses to which derivatives of cellulose only have been applied.

The new proteld compositions are obtained by treating proteid substances with .alkalies and the alkali-albumens thus obtained with bisulfid of carbon (65,).

The process can be applied to all albuminoids (or proteids). For instance, fibrin casein, wool waste, silk andsilk waste, myosin, gut, vegetable albumens, horn, hide,

leather and itswaste can be treated. As an fibrin thus obtained is cut up and submitted to the action of bisulfid of carbon for 30 to minutes. During this operation the product turns yellow, and the exce$ of bisulfid of carbon is then removed for instance by so in the. orm of a means of a vacuum. After some time for example 8 to 15 hours the mass dissolves in the water which it contains, itbeing a more or less viscous solution soluble in water.

The following is an example of the proportions of the substances that may be employed: fibrin 100 parts, 10% solution of sodium hydrate 100 parts, bisulfid of carbon 20 to 30 arts.

The i and bisulfid of carbon are employed succesively as above described.

When the proteid solutions thus obtained are allowed to stand for some days they undergo condensation, whereby they become more and more viscous and less soluble in Water, finall solidifying if permitted to do slightly elastic and Horny mass. In practice 1t is preferred to utilize the solutions as soon as possible after their'preparation, and in any case before they commence to coagulate. If necessary the solutions may be preserved for a month between 0 and 5 C.

The above mentioned protcid solutions have the property of being coagulated and precipitated by different salts \vhich'are known to coagulate alkali-albumens. Ammonia salts such as sulfate and ferrocyanid of ammonium can be used to precipitate the solutions and said solutions are decomposed by diluted acids while regenerating a proteid substance.

The solutions treated with a solution of acetate of lead produce a red precipitate insolublein acetic acid, which is found to be a combination of CS protein and lead. This combination is unstable, decomposing into albumen and lead sulfid. Known xanthates, such for example as SNa and that of phenol a are also precipitated by acid acetate of lead onmore by keeping them at a temperature while iving a combination of alcohol, sulfid I V I of car 11 and of lead in the first case and phenol, sulfid of carbon and lead in the alcohol and PbS or into phenol and PbS respectively. The protein solutions may therefore be considered as proteld xanthates arising from the substitution of an atom ofhy drogen of the proteid substance by the radical CS Na. Itwill be seenthat these combinations while deriving substances difl'ering in a high degree from cellulose have a certain rosemblance in some of their properties to 2mmthates of cellulose or viscose. These solutions of proteid xanthates may be mixed 1n any proportion with solutions ofcellulose xanthates to produce mixtures of proteocellulose-xanthates' The mixed solutions are preci itated by ammonia salts and decomby strong acids while regenerating a mixture of cellulose and protein.

As regards the chemical character of these products, it may be pointed out that salts of ammonium, and particularly sulfid of amdilute sulfuric acid there is obtained a prod uct which reacts both for protein and cellulose. If for example the product, which maly be in the form of a precipitate; filament, pe icle, etc., be treated by Millons reagent (nitrate of mercury), in aheated state, it

' will be found to turn'red, the color disappeering by subsequent boiling. It is also ound that the nitrogen content of the prodnot is substantially proportionate to the proportion of protein on ally introduced into the solution. The ce lulos'e can be distinguished by treating the filament with concentrated sulfuric acid, the resulting solution after neutralization by soda reducing Fehlings liquor.

The proteocellulosic-xanthate solutions can be applied to different industrial uses such as the manufacture of thread, silk,hair filaments,-pellicles, 'molded and compressed tissues, etc. For instance, silky threads or filaments can be obtained by passing the substance through a draw late and coagulating it in a neutral bath of sulfate of ammonia and treating the threads obtained with dilute sulfuric acid.

Other neutral salts, as for example theammonium salts, can be'used for the above purpose, as-also may other strong acids as hydrochloric acid.

A combination of proteo-cellulose xanthates can thus be obtained b treatin a mixture. of alkali-fibrin and a1 ali-cellu ose with bisulfid of carbon. The'proportions may be as desired, a mixture containing 50 to of alkali-fibrin being commonly used.

The proteo-cellulosic threads obtained as above described can be subsequently subjected to the action of baths for, as it were,.

tannin the threads and giving them reater strengt elasticity and suppleness; or this purpose the following so ution's can be employed; (a) Aqueous solutions of 2 to 5% of qumone. (b) Aqueous solutions of 2 to 5% of 'hydroquinone. (c) Aqueous solutions f 10 to 50 per thousand of tannin'.. e 60 thread is soaked for acertain time or until imgregnation iscom lete in-these solutions all then washed an' driediv The- :thr'ead is immersed fori'some minutes, the time va ing with the temperature and other con i- In order to impart to the thread water re sisting qualities and at the same time tenacity when in the dry state, it can be treated by methods as follows: (a) Immersion in dilute baths of bichromate of potash, say three to five parts cr' 1000. (b) Treatment by condensing anti dehydrating agents for the purpose of condensing the proteo-cellulose molecule for example a 5% solution of formal in presence of a dehydrating agent such as acetic anhydrid diluted with crystallizable acetic acid, the preferred proportions being of acetic acid to 5% of acetic anhydrid).

The proteo -cellulosic products obtained as above described are solid, elastic and tenacious, insoluble in' water andin or nic sol,- vents, but soluble in concentrate sulfuric acid, forming a homogeneous viscous paste which reddens in a few hours .When exposed to the air. When heated they commence to carbonize at about 200 C. and burn in air with a smell of burnin horn. Submitted to the action of a 20% so a solution the product is partly dissolved with decomposition,

the resulting alkaline solution having the following properties; (a) with solutions of concentrated ammonium sulfate yields a gelatinous'preci itate solublein water; b) with strong acid; in a diluted state it yie ds a gelatinous precipitate insoluble in water; (0) acetate of lead gives a red flaky recipitate of proteo-xanthate of lead, w ich upon boiling gives a black precipitate of lead sulfate mixed with protein.

What I claim as my lnvention and desire to secure by Letters Patent of the United States is 1. A process of obtaining V roteo-cellulosic derivatives, consisting m su mitting a rotein substance to the successive action 0 al--.

kalies and of bisulfid of carbonto produce a viscous solution, adding to the solution xanthate of cellulose, precipitating the solution by means of an ammonium. salt, and decomposing the product thus obtained by a strong acid in a diluted state. Q g

, '2. A rocess of obtaining proteo-cellulosic derivatives, consisting in submitting. a protein substance to the successive action of alkalies and (pf-bisulfid of carbon to produce a viscous solution, adding to the solution xanthate of cellulose, precipitating the solution b means of an ammonium salt, decomposing tli e product thus obtained by a strongjac' in a diluted state, and submitting the product; thus obtained totheaction of solutions of tanning 3'. A i proce ss of obtaining roteo-cellulosic derivatives, consisting in en mitting a roteinsubstanceto the successive action 0 alkalies and of bisulfid of. carbon'to' produce a the product thus obtained by a strong acid In witness whereof I have signed this in a diluted state, submitting the product specification in the presence of two witnesses.

thus obtained to the action of solutions of tann'ing substances and finally to the action 5 of condensing and dehydrating agents to increase the resistance and elasticity of the product.

'- Signed and sealedthis 4th day of Octoher, A. D., 1910.

HENRI LOUIS JOSEPH CHAVASSIEU.

, Witnesses:

JEAN GERMAIN, GUILLAUME PIooHE.

It is hereby certified that in Patent So. 950,4t35, granted February 22; 1910;

upon the application of Henri Louis Joseph Chavassieu, of Lyon, France, for an improvement in Processes of Ohtaining Proteo-Cellulosic Products} errors appear v in the printed specification requiring correction, as follows: Page 1, line 113?, the word sulfide should read sizlfdte; page 2,.line 5, the .word sulfid shouldread sulfate, and same page, line 100, the word 5 sulfate 'should' read mdfid; and that the a said Letters Patent should beread with these corrections therein that the same may conform to the record of in the Patent Oflice.

E; B. Moons,

[smn] I Commissioner of Patents.

the product thus obtained by a strong acid In witness whereof I have signed this in a diluted state, submitting the product specification in the presence of two witnesses.

thus obtained to the action of solutions of tann'ing substances and finally to the action 5 of condensing and dehydrating agents to increase the resistance and elasticity of the product.

'- Signed and sealedthis 4th day of Octoher, A. D., 1910.

HENRI LOUIS JOSEPH CHAVASSIEU.

, Witnesses:

JEAN GERMAIN, GUILLAUME PIooHE.

It is hereby certified that in Patent So. 950,4t35, granted February 22; 1910;

upon the application of Henri Louis Joseph Chavassieu, of Lyon, France, for an improvement in Processes of Ohtaining Proteo-Cellulosic Products} errors appear v in the printed specification requiring correction, as follows: Page 1, line 113?, the word sulfide should read sizlfdte; page 2,.line 5, the .word sulfid shouldread sulfate, and same page, line 100, the word 5 sulfate 'should' read mdfid; and that the a said Letters Patent should beread with these corrections therein that the same may conform to the record of in the Patent Oflice.

E; B. Moons,

[smn] I Commissioner of Patents.

Corrections in Letters Patent No. 950,435.

It is hereby certified that in Letters Patent No. 950,435, granted February 22, 1910,

upon the application of Henri Louis Joseph Chavassieu, of Lyon. France, for an improvement in f Processes of Obtaining Proteo -Cellulosic Products, errors anpear in the printed specification requiring correction, as follows: Page 1, line 112, the word sulfid should read sulfate, page 2, line 5, the word sulfid should read sulfate, and same page, line 100, the word sulfate should read sulfid; and that the said Letters Patent should be read with these corrections therein that the same may conform to the record of the case in the Patent Oflice.

Signed and sealed this 4th day of October, A. D., 1910.

' E. B. MOORE,

Commie-simmer of Patents.

[SEAL] 

